Hydrocracking catalyst, its method of making, and method of use
A hydrocracking catalyst comprises an active cracking support. The active cracking support comprises a post-modified zeolite framework having zirconium atoms and titanium atoms substituting for aluminum atoms; wherein: a portion of the zirconium atom are substituted in the post-modified zeolite via 4-coordination; a portion of the zirconium atom are grafted to the post-modified zeolite via 5-coordination; and the titanium atoms are substituted in the post-modified zeolite framework via 4-coordination.
1 . A hydrocracking catalyst comprising an active cracking support;
the active cracking support comprises a post-modified zeolite framework having zirconium atoms and titanium atoms substituting for aluminum atoms; wherein:
the post-modified zeolite has an ultra-stable Y (USY) framework structure;
a portion of the zirconium atom are substituted in the post-modified zeolite via 4-coordination;
a portion of the zirconium atom are grafted to the post-modified zeolite via 5-coordination; and
the titanium atoms are substituted in the post-modified zeolite framework via 4-coordination.
2 . The hydrocracking catalyst of claim 1 , wherein the post-modified zeolite has a specific surface area of from 600 m 2 /g to 900 m 2 /g.
3 . The hydrocracking catalyst of claim 1 , wherein the post-modified zeolite has a crystal lattice constant of from 2.430 nm to 2.450 nm.
4 . The hydrocracking catalyst of claim 1 , wherein the post-modified zeolite has a molar ratio of SiO 2 to Al 2 O 3 of from 5 to 100.
5 . The hydrocracking catalyst of claim 1 , wherein the hydrocracking catalyst further comprises a hydrogenative component.
6 . The hydrocracking catalyst of claim 5 , wherein the hydrocracking catalyst comprises from 0.1 wt. % to 40 wt. % of the hydrogenative component.
7 . The hydrocracking catalyst of claim 5 , wherein the hydrogenative component comprises at least one metal from IUPAC groups 6 or 8.
8 . The hydrocracking catalyst of claim 5 , wherein the hydrogenative component comprises one or more metals selected from the group consisting of cobalt, nickel, palladium, platinum, molybdenum, or tungsten.
9 . The hydrocracking catalyst of claim 1 , wherein the zeolite has a specific surface area of from 600 m 2 /g to 900 m 2 /g; a crystal lattice constant of from 2.430 nm to 2.450 nm; and a molar ratio of SiO 2 to Al 2 O 3 of from 5 to 100.
10 . A method of producing a hydrocracking active cracking support comprising
providing an acidified zeolite suspension comprising a zeolite framework;
introducing a titanium compound to the acidified zeolite suspension to isomorphically substitute titanium via 4-coordination onto the zeolite framework, thereby producing a titanium substituted zeolite framework; and
then introducing a zirconium compound to the titanium substituted zeolite framework to
graft a portion of the zirconium atoms onto the zeolite framework via 5-coordination, and
isomorphically substitute a portion of the zirconium atoms via 4-coordination onto the zeolite framework, thereby producing the hydrocracking active cracking support, wherein a time interval between the introduction of the titanium compound and the introduction of the zirconium compound is at least 0.5 hours.
11 . The method of claim 10 , wherein a time interval between the introduction of the titanium compound and the introduction of the zirconium compound is from 0.5 hours to 5 hours.
12 . The method of claim 10 , wherein the acidified suspension has a liquid/solid mass ratio of from 5 to 15.
13 . The method of claim 10 , wherein the acid is an inorganic acid or an organic acid.
14 . The method of claim 10 , wherein a pH of the acidified suspension is less than 2.
15 . The method of claim 10 , wherein the zeolite is dried and subsequently heat treated at from 500° C. to 700° C.
16 . The method of claim 10 , wherein:
a time interval between the introduction of the titanium compound and the introduction of the zirconium compound is from 0.5 hours to 5 hours;
the acidified suspension has a liquid/solid mass ratio of from 5 to 15;
a pH of the acidified suspension is less than 2.0; and
the zeolite is heat treated at from 500° C. to 700° C.
17 . A method of hydrocracking a hydrocarbon feed, the method comprising contacting the hydrocarbon feed with hydrogen and a hydrocracking catalyst under hydrocracking conditions; wherein the hydrocracking catalyst comprises an active cracking support;
the active cracking support comprises a post-modified zeolite framework having zirconium atoms and titanium atoms substituting for aluminum atoms; wherein
the post-modified zeolite has an ultra-stable Y (USY) framework structure;
a portion of the zirconium atoms are grafted to the post-modified zeolite framework via 5-coordination;
a portion of the zirconium atoms are 4-coordinated in the post-modified zeolite framework; and
the titanium atoms are 4-coordinated in post-modified zeolite framework.
18 . The method of claim 17 , wherein the hydrocarbon feed comprises a heavy hydrocarbon oil.
19 . A hydrocracking catalyst comprising the hydrocracking active cracking support of claim 10 .
20 . The method of claim 10 , wherein the zeolite framework has an ultra-stable Y (USY) framework structure.